Beta-propiolactone based copolymers containing biogenic carbon, methods for their production and uses thereof

ABSTRACT

Provided herein are methods and systems for producing biodegradable beta-propiolactone-based polyester polymers from renewable EO and CO on an industrial scale.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. patentapplication Ser. No. 16/178,214, filed on Nov. 1, 2018, published asU.S. Publication No. US2019/0071538, which is a divisional applicationthat claims priority to and the benefit of U.S. patent application Ser.No. 15/369,764, entitled “Beta-Propiolactone Based Copolymers ContainingBiogenic Carbon, Methods For Their Production And Uses Thereof,” filedon Dec. 5, 2016, each of which is herein incorporated by reference intheir entirety.

FIELD

The present disclosure relates generally to polymeric materials and theproduction of polymers derived from beta-propiolactone that is producedfrom renewable ethylene oxide and carbon monoxide feed sources. Morespecifically this invention relates to propiolactone copolymers suitablefor use in thermoplastic applications, moisture barrier applications,packaging application etc. and as chemical precursors along with methodsof producing such polymers.

BACKGROUND

Poly(beta-propiolactone) is an aliphatic polyester and can be completelybio-degradable to CO2 and water. Poly(beta-propiolactone) has potentialapplications in many different areas including medical, pharmaceuticaland packaging industries due to their biodegradability. The presentinvention relates to producing co-polymers from beta-propiolactone and aco-monomer.

Polypropiolactone (PPL) is a biodegradable polymer that can be used inmany applications such as fibers and films. It is also known that PPLmay be thermally degraded to high purity acrylic acid which is in highdemand for the production of polyacrylic acid-based superabsorbentpolymers, detergent co-builders, dispersants, flocculants andthickeners.

The recent advances in carbonylation of epoxides disclosed in U.S. Pat.No. 6,852,865 and the efficient ring opening polymerization ofbeta-propiolactone opened up the efficient synthetic routes topoly(beta-propiolactone) from ethylene oxide and CO. However, there arepractical problems, preventing highly amorphous poly(beta-lactone) fromindustrially processed. Highly amorphous poly(beta-propiolactone) hasbeen nearly impossible to produce at reasonable operating rates due toits low melting point.

There is a need to provide highly biodegradable polymers for productsthat have a short usable life and thereafter need rapid assimilationback into the environment. Production of such polymers from renewablesources and recycled sources will further reduce their environment footprint. As such, there remains a need for methods of producing aco-polymer of beta-propiolactone, having improved processability andthermal stability.

BRIEF SUMMARY OF THE INVENTION

Polymerization of poly-propiolactone (PPL) from beta-propiolactone (bPL)is generally known, however the present invention is directed to systemsand methods for including bPL obtained from the carbonylation ofethylene oxide (EO) and preferably carbon monoxide (CO) from bio-masssources into lactone based copolymers. Renewably sourced bPL may bepolymerized to produce PPL homo polymers and PPL heteropolymers and PPLpolymer derivatives. These uniquely sustainable polymers are highlybiodegradable while still meeting the performance requirements for thematerials demanded in many applications. Such bPL derived polymersretain the biodegradability of the beta-propiolactone constituents andprovide an environmentally friendly benefit to many applications thatnow use polymers with poor biodegrade properties and poor bio-basedcarbon content. Combining sourcing of the bPL copolymer precursors fromEO containing carbon from bio-mass sources and preferably CO frombio-mass sources of provides significant and needed environmentbenefits.

The ability to use bPL derived at least in part from EO and COcontaining renewable and recycled carbon magnifies the environmentalbenefit obtained from the polymers of this invention and the productionmethods of this invention.

The present invention relates to producing co-polymers frombeta-propiolactone and a co-monomer wherein at least thebeta-propiolactone has a bio-content.

Some aspects of this invention provide a linear bPL copolymer producedfrom a feed stream of bPL and a comonomer where the bPL is obtained bythe carbonylation of EO and CO and wherein at least a portion of the EOcontains carbon from bio-mass sources, also known as biogenic carbon. Inpreferred aspects of this invention all of the EO is derived frombiogenic carbon. In highly preferred aspects of this invention all ofthe EO and CO is derived from biogenic carbon.

Certain aspects of this invention provide a method of producing a bPLcopolymer, comprising combining bPL and an initiator in the presence ofa metal cation and a comonomer to produce the bPL based copolymer(hereinafter also referred to as the “copolymer”) wherein the bPL isproduced by the carbonylation of EO and CO sourced at least in part fromone or more renewable feed stocks. In preferred aspects of thisinvention all of the EO is derived from renewable sources. In otherpreferred aspects of this invention at least a portion of the CO isderived from renewable sources. In highly preferred aspects of thisinvention all of the EO and CO are derived from renewable sources.

In a broad embodiment, the bPL co-polymer is produced by ring openingpolymerization of biogenic beta-propiolactone and a co-monomer. In apreferred embodiment the co-monomer is selected from the groupcomprising lactones and anhydrides.

In some aspects, the co-monomer is a lactone having a greater number ofcarbon atoms than bPL and is herein referred to as a higher lactone.

In some aspects, the co-monomer is a beta-lactone having a greaternumber of carbon atoms bPL and herein referred to as a higherbeta-lactone.

In further aspects, suitable higher beta-lactones for theco-polymerization include beta-butyrolactone, beta-valerolactone,beta-heptanolactone, beta-tridecanolactone,cis-3,4-dimethyloxetan-2-one, 4-(butoxymethyl)-2-oxetanone,4-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-2-oxetanone,4-[(2-propen-1-yloxy)methyl]-2-oxetanone,4-[(benzoyloxy)methyl]-2-Oxetanone.

In some aspects of this invention, the co-monomer is a cyclic anhydride.In preferred aspects, the cyclic anhydrides include succinic anhydride,and maleic anhydride.

In some embodiments, the co-polymerization of beta-lactones and cyclicanhydride is performed in the presence of polymerization catalyst. Thepolymerization catalyst initiates the ring opening polymerization ofbeta-lactones or cyclic anhydrides to produce co-polymers. A broad rangeof polymerization catalysts can be used for the initiation of the ringopening polymerization.

In another aspect this invention is a linear polyester comprising a bPLbased copolymer having linear chains of repeating (O(CH2)2CO)X unitscontaining carbon and oxygen atoms provided by a bPL feed produced fromthe carbonylation of EO containing carbon and oxygen atoms thatoriginate from a renewable source. Where X is a comonomer unit fromparagraph 0014 and/or 0015. In another variation of the invention thecarbon source is CO that contains carbon and oxygen atoms that originatefrom a renewable source. In another variation of the invention all ofthe atoms in EO are derived from a renewable source. In anothervariation of the invention all of the atoms in the EO and CO originatefrom a renewable source. In certain variations the polymer chains haveopposing end groups of initiator and a cation. In other variations theinitiator comprises an anionic nucleophile.

In preferred applications of this invention the copolymers describedherein, may be suitable for use as thermoplastics. PPL polymers areknown to have relatively low melting points. The melting point of thethermoplastics obtained by this invention may be adjusted by theselection of the co-monomer. Thus, the thermoplastics of this inventionmay use as fiber, films, and structural components.

Structural components that may be formed using the copolymers of thisinvention include any article requiring rigidity or load bearingcapacity. Examples of Structural components include household items,furniture, building components, sculptures and machinery assemblies. Forapplication as structural components, the copolymer of this inventionthe comonomers will be selected to provide the copolymer with arelatively high melting temperature.

Fibers and films application for the copolymers of this invention canalso include a wide range of products. Such products can includebiodegradable packaging and biodegradable moisture barriers formultilayer that comprise a component of diapers, adult incontinenceproducts, or feminine hygiene products. In these applications thecomonomers will typically be selected to give copolymer a relatively lowmelting temperature.

In preferred applications of this invention the copolymers describedherein, may be suitable for use as thermoplastics having low meltingtemperatures. Such thermoplastics may have use as molding materials.

In another embodiment this invention is a method to produce a bPLcopolymer. Thus in various aspects, production systems/productionprocesses for producing the bPL copolymer are provided.

Accordingly in one aspect the invention is a method for producing a bPLcopolymer having from renewable carbon content. In this aspect one feedcomponent is a bPL monomer derived having biogenic carbon content.Another feed component is a comonomer. The method combines the monomerand comonomer with polymerization catalyst in a polymerization reactionzone at polymerization conditions to produce a bPL based copolymer thatis recovered as at least part of a product stream. Preferably at least aportion of the bPL monomer feed component comprises bPL produced by thecarbonylation of ethylene oxide having a bio-content of at least 10%with carbon monoxide that optionally has a bio-content of at least 10%and a comonomer derived from a lactone other than beta-propiolactone.

In another aspect, the method of this invention combines the bPLmonomer, comonomer and optional polymerization catalyst or initiator toproduce the bPL based copolymer. This can be done in one or morereactors in series.

In another aspect, method of this invention a product stream containingthe bPL based co-polymer includes at least one of the bPL monomer, thecomonomer and the polymerization catalyst is recovered from thepolymerization reaction zone. In this aspect at least a portion of thebPL based copolymer is separated from any bPL monomer, the comonomerand/or the polymerization catalyst and a purified bPL based copolymerhaving a higher bPL content than the bPL product stream is recovered. Ina preferred form of this aspect at least a portion of any bPL monomer,the comonomer and/or polymerization catalyst separated from the productstream is recycled to the polymerization reaction zone.

In a further aspect, the polymerization zone include multiplepolymerization reactors and one or more intermediate product streamcomprising the bPL based polymer, bPL monomer, the comonomer and thepolymerization catalyst pass from one polymerization reactor to anotherpolymerization reactor. The polymerization reactors in this aspect haveone or more inlets and one or more outlets and one or more transferconduits to transfer intermediate product stream between thepolymerization reactors.

In another aspect the invention is process for producing a sustainablebPL based copolymer comprising beta-propiolactone monomers and higherlactone monomers that starts with the production of the bPL monomershaving a suitable bio-content. The process begins with combining EOhaving a bio-content, CO preferably having bio-content, carbonylationcatalyst, and solvent in a carbonylation reaction zone at carbonylationconditions; producing bPL; and recovering at least a portion of the bPLas a bPL output stream. At least a portion of the bPL output streampasses to a bPL purification zone that produces a recycle streamcomprising at least one of EO, CO, carbonylation catalyst, and solventand the bPL output stream; and, at least a portion of the bPL recyclestream is returned to the carbonylation reaction zone. This aspectcombines feed components comprising a bPL polymerization initiator and acation donor, and at least a portion of bPL output stream and contactsthe feed components in a polymerization reactor at polymerizationconditions to produce a bPL based copolymer. At least a portion of thebPL based copolymer is recovered as a This aspect combines feedcomponents comprising a bPL polymerization initiator and a cation donor,and at least a portion of bPL output stream and contacts the feedcomponents in a polymerization reactor at polymerization conditions toproduce a bPL based copolymer. At least a portion of the bPL basedcopolymer is recovered as a bPL copolymer output stream.

The present application can be best understood by reference to thefollowing description.

DETAILED DESCRIPTION

The following description sets forth exemplary methods, parameters andthe like. It should be recognized, however, that such description is notintended as a limitation on the scope of the present disclosure but isinstead provided as a description of exemplary aspects.

Definitions

The terms bio-content and bio-based content mean biogenic carbon alsoknown as bio-mass derived carbon.

In some variations, bio-content (also referred to as “bio-basedcontent”) can be determined based on the following:

% Bio-content or Bio-based content=

[Bio (Organic) Carbon]/[Total (Organic) Carbon]100%,

as determined by ASTM D6866 (Standard Test Methods for Determining theBio-based (biogenic) Content of Solid, Liquid, and Gaseous Samples UsingRadiocarbon Analysis).

The bio-content of the polymers may depend based on the bio-content ofthe beta-propiolactone used. For example, in some variations of themethods described herein, the beta-propiolactone used to produce thepolymers described herein may have a bio-content of greater than 0%, andless than 100%. In certain variations of the methods described herein,the beta-propiolactone used to produce the polymers described herein mayhave a bio-content of at least 10%, at least 20%, at least 30%, at least40%, at least 50%, at least 60%, at least 70%, at least 80%, at least90%, at least 95%, at least 96%, at least 97%, at least 98%, at least99%, at least 99.5%, at least 99.9%, at least 99.99%, or 100%. Incertain variations, beta-propiolactone derived from renewable sources isused. In other variations, at least a portion of the beta-propiolactoneused is derived from renewable sources, and at least a portion of thebeta-propiolactone is derived from non-renewable sources.

The bio-content of the beta-propiolactone may depend on, for example,the bio-content of the ethylene oxide and carbon monoxide used. In somevariations, both ethylene oxide and carbon monoxide are derived frombiogenic or bio-mass based carbon sources.

Biodegradability

In some variations of the foregoing, the polymer has a biodegradabilityof at least 10%, at least 20%, at least 30%, at least 40%, at least 50%,at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, atleast 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, atleast 99.9%, at least 99.99%, or 100%.

Biodegradable and biodegradability is as defined and determined based onASTM D5338-15 (Standard Test Method for Determining AerobicBiodegradation of Plastic Materials Under Controlled CompostingConditions, Incorporating Thermophilic Temperatures).

In other aspects the product stream comprises at least one of bPLpolymerization initiator, and cation donor and at least a portion of theproduct stream passes to a purification zone. The purification zonerecovers at least one of beta-propiolactone, bPL polymerizationinitiator and cation donor from the product stream in one or morerecycle streams and produces a purified product stream and at least aportion of a recycle stream is returned to the polymerization reactionzone to provide a purified product stream comprising a bPL basedcopolymer in a higher concentration than the product stream is recoveredfrom the process. In other aspects the polymerization reaction zonecomprises multiple reactors, an upstream reactor produces the productstream; at least a portion of the purified product stream enters adownstream reactor and a high purity product stream is recovered fromthe downstream reactor. A portion of the recycle stream may pass to theupstream reactor.

Definitions of specific functional groups and chemical terms aredescribed in more detail below. The chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 75^(th) Ed., inside cover, andspecific functional groups are generally defined as described therein.Additionally, general principles of organic chemistry, as well asspecific functional moieties and reactivity, are described in OrganicChemistry, Thomas Sorrell, University Science Books, Sausalito, 1999;Smith and March March's Advanced Organic Chemistry, 5^(th) Edition, JohnWiley & Sons, Inc., New York, 2001; Larock, Comprehensive OrganicTransformations, VCH Publishers, Inc., New York, 1989; Carruthers, SomeModern Methods of Organic Synthesis, 3^(rd) Edition, CambridgeUniversity Press, Cambridge, 1987; the entire contents of each of whichare incorporated herein by reference.

The terms “halo” and “halogen” as used herein refer to an atom selectedfrom fluorine (fluoro, —F), chlorine (chloro, —Cl), bromine (bromo,—Br), and iodine (iodo, —I).

The terms “halide” as used herein refer to a halogen bearing a negativecharge selected from fluoride —F⁻, chloride —Cl⁻, bromide —Br⁻, andiodide —I⁻.

The term “aliphatic” or “aliphatic group”, as used herein, denotes ahydrocarbon moiety that may be straight-chain (i.e., unbranched),branched, or cyclic (including fused, bridging, and spiro-fusedpolycyclic) and may be completely saturated or may contain one or moreunits of unsaturation, but which is not aromatic. Unless otherwisespecified, aliphatic groups contain 1-30 carbon atoms. In some aspects,aliphatic groups contain 1-12 carbon atoms. In some aspects, aliphaticgroups contain 1-8 carbon atoms. In some aspects, aliphatic groupscontain 1-6 carbon atoms. In some aspects, aliphatic groups contain 1-5carbon atoms, in some aspects, aliphatic groups contain 1-4 carbonatoms, in yet other aspects aliphatic groups contain 1-3 carbon atoms,and in yet other aspects, aliphatic groups contain 1-2 carbon atoms.Suitable aliphatic groups include, but are not limited to, linear orbranched, alkyl, alkenyl, and alkynyl groups, and hybrids thereof suchas (cycloalkyl)alkyl, (cycloalkenyl)alkyl or (cycloalkyl)alkenyl.

The term “heteroaliphatic,” as used herein, refers to aliphatic groupswherein one or more carbon atoms are independently replaced by one ormore atoms selected from the group consisting of oxygen, sulfur,nitrogen, phosphorus, or boron. In some aspects, one or two carbon atomsare independently replaced by one or more of oxygen, sulfur, nitrogen,or phosphorus. Heteroaliphatic groups may be substituted orunsubstituted, branched or unbranched, cyclic or acyclic, and include“heterocycle,” “heterocyclyl,” “heterocycloaliphatic,” or “heterocyclic”groups.

The term “acrylate” or “acrylates” as used herein refer to any acylgroup having a vinyl group adjacent to the acyl carbonyl. The termsencompass mono-, di- and tri-substituted vinyl groups. Examples ofacrylates include, but are not limited to: acrylate, methacrylate,ethacrylate, cinnamate (3-phenylacrylate), crotonate, tiglate, andsenecioate.

The term “polymer”, as used herein, refers to a molecule of highrelative molecular mass, the structure of which comprises the multiplerepetitions of units derived, actually or conceptually, from moleculesof low relative molecular mass. In some aspects, a polymer is comprisedof only one monomer species (e.g., polyEO). In some aspects, a polymeris a copolymer, terpolymer, heteropolymer, block copolymer, or taperedheteropolymer of one or more epoxides.

The term “unsaturated”, as used herein, means that a moiety has one ormore double or triple bonds.

The terms “cycloaliphatic”, “carbocycle”, or “carbocyclic”, used aloneor as part of a larger moiety, refer to a saturated or partiallyunsaturated cyclic aliphatic monocyclic, bicyclic, or polycyclic ringsystems, as described herein, having from 3 to 12 members, wherein thealiphatic ring system is optionally substituted as defined above anddescribed herein. Cycloaliphatic groups include, without limitation,cyclopropyl, cyclobutyl, cyclopentyl, cyclopentenyl, cyclohexyl,cyclohexenyl, cycloheptyl, cycloheptenyl, cyclooctyl, cyclooctenyl, andcyclooctadienyl. In some aspects, the cycloalkyl has 3-6 carbons.Representative carbocyles include cyclopropane, cyclobutane,cyclopentane, cyclohexane, bicyclo[2,2,1]heptane, norbornene, phenyl,cyclohexene, naphthalene, and spiro[4.5]decane. The terms“cycloaliphatic”, “carbocycle” or “carbocyclic” also include aliphaticrings that are fused to one or more aromatic or nonaromatic rings, suchas decahydronaphthyl or tetrahydronaphthyl, where the radical or pointof attachment is on the aliphatic ring. In some aspects, a carbocyclicgroup is bicyclic. In some aspects, a carbocyclic group is tricyclic. Insome aspects, a carbocyclic group is polycyclic.

The term “alkyl,” as used herein, refers to saturated, straight- orbranched-chain hydrocarbon radicals derived from an aliphatic moietycontaining between one and six carbon atoms by removal of a singlehydrogen atom. Unless otherwise specified, alkyl groups contain 1-12carbon atoms. In some aspects, alkyl groups contain 1-8 carbon atoms. Insome aspects, alkyl groups contain 1-6 carbon atoms. In some aspects,alkyl groups contain 1-5 carbon atoms, in some aspects, alkyl groupscontain 1-4 carbon atoms, in yet other aspects, alkyl groups contain 1-3carbon atoms, and in yet other aspects alkyl groups contain 1-2 carbonatoms. Examples of alkyl radicals include, but are not limited to,methyl, ethyl, n-propyl, isopropyl, n-butyl, iso-butyl, sec-butyl,sec-pentyl, iso-pentyl, tert-butyl, n-pentyl, neopentyl, n-hexyl,sec-hexyl, n-heptyl, n-octyl, n-decyl, n-undecyl, dodecyl, and the like.

The term “aryl” used alone or as part of a larger moiety as in“aralkyl”, “aralkoxy”, or “aryloxyalkyl”, refers to monocyclic andpolycyclic ring systems having a total of five to 20 ring members,wherein at least one ring in the system is aromatic and wherein eachring in the system contains three to twelve ring members. The term“aryl” may be used interchangeably with the term “aryl ring”. In someaspects, “aryl” refers to an aromatic ring system which includes, but isnot limited to, phenyl, naphthyl, anthracyl and the like, which may bearone or more substituents. Also included within the scope of the term“aryl”, as it is used herein, is a group in which an aromatic ring isfused to one or more additional rings, such as benzofuranyl, indanyl,phthalimidyl, naphthimidyl, phenanthridinyl, or tetrahydronaphthyl, andthe like.

The terms “heteroaryl” and “heteroar-”, used alone or as part of alarger moiety, e.g., “heteroaralkyl”, or “heteroaralkoxy”, refer togroups having 5 to 14 ring atoms, preferably 5, 6, 9 or 10 ring atoms;having 6, 10, or 14 π electrons shared in a cyclic array; and having, inaddition to carbon atoms, from one to five heteroatoms. The term“heteroatom” refers to nitrogen, oxygen, or sulfur, and includes anyoxidized form of nitrogen or sulfur, and any quaternized form of a basicnitrogen. Heteroaryl groups include, without limitation, thienyl,furanyl, pyrrolyl, imidazolyl, pyrazolyl, triazolyl, tetrazolyl,oxazolyl, isoxazolyl, oxadiazolyl, thiazolyl, isothiazolyl,thiadiazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, indolizinyl,purinyl, naphthyridinyl, benzofuranyl and pteridinyl. The terms“heteroaryl” and “heteroar-”, as used herein, also include groups inwhich a heteroaromatic ring is fused to one or more aryl,cycloaliphatic, or heterocyclyl rings, where the radical or point ofattachment is on the heteroaromatic ring. Non-limiting examples includeindolyl, isoindolyl, benzothienyl, benzofuranyl, dibenzofuranyl,indazolyl, benzimidazolyl, benzthiazolyl, quinolyl, isoquinolyl,cinnolinyl, phthalazinyl, quinazolinyl, quinoxalinyl, 4H-quinolizinyl,carbazolyl, acridinyl, phenazinyl, phenothiazinyl, phenoxazinyl,tetrahydroquinolinyl, tetrahydroisoquinolinyl, andpyrido[2,3-b]-1,4-oxazin-3(4H)-one. A heteroaryl group may be monocyclicor bicyclic. The term “heteroaryl” may be used interchangeably with theterms “heteroaryl ring”, “heteroaryl group”, or “heteroaromatic”, any ofwhich terms include rings that are optionally substituted. The term“heteroaralkyl” refers to an alkyl group substituted by a heteroaryl,wherein the alkyl and heteroaryl portions independently are optionallysubstituted.

As used herein, the terms “heterocycle”, “heterocyclyl”, “heterocyclicradical”, and “heterocyclic ring” are used interchangeably and refer toa stable 5- to 7-membered monocyclic or 7- to 14-membered bicyclicheterocyclic moiety that is either saturated or partially unsaturated,and having, in addition to carbon atoms, one or more, preferably one tofour, heteroatoms, as defined above. When used in reference to a ringatom of a heterocycle, the term “nitrogen” includes a substitutednitrogen. As an example, in a saturated or partially unsaturated ringhaving 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, thenitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as inpyrrolidinyl), or ⁺NR (as in N-substituted pyrrolidinyl).

A heterocyclic ring can be attached to its pendant group at anyheteroatom or carbon atom that results in a stable structure and any ofthe ring atoms can be optionally substituted. Examples of such saturatedor partially unsaturated heterocyclic radicals include, withoutlimitation, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl,pyrrolidonyl, piperidinyl, pyrrolinyl, tetrahydroquinolinyl,tetrahydroisoquinolinyl, decahydroquinolinyl, oxazolidinyl, piperazinyl,dioxanyl, dioxolanyl, diazepinyl, oxazepinyl, thiazepinyl, morpholinyl,and quinuclidinyl. The terms “heterocycle”, “heterocyclyl”,“heterocyclyl ring”, “heterocyclic group”, “heterocyclic moiety”, and“heterocyclic radical”, are used interchangeably herein, and alsoinclude groups in which a heterocyclyl ring is fused to one or morearyl, heteroaryl, or cycloaliphatic rings, such as indolinyl,3H-indolyl, chromanyl, phenanthridinyl, or tetrahydroquinolinyl, wherethe radical or point of attachment is on the heterocyclyl ring. Aheterocyclyl group may be mono- or bicyclic. The term“heterocyclylalkyl” refers to an alkyl group substituted by aheterocyclyl, wherein the alkyl and heterocyclyl portions independentlyare optionally substituted.

As used herein, the term “partially unsaturated” refers to a ring moietythat includes at least one double or triple bond. The term “partiallyunsaturated” is intended to encompass rings having multiple sites ofunsaturation, but is not intended to include aryl or heteroarylmoieties, as herein defined.

As described herein, compounds may contain “optionally substituted”moieties. In general, the term “substituted”, whether preceded by theterm “optionally” or not, means that one or more hydrogens of thedesignated moiety are replaced with a suitable substituent. Unlessotherwise indicated, an “optionally substituted” group may have asuitable substituent at each substitutable position of the group, andwhen more than one position in any given structure may be substitutedwith more than one substituent selected from a specified group, thesubstituent may be either the same or different at every position.Combinations of substituents envisioned may include those that result inthe formation of stable or chemically feasible compounds. The term“stable”, as used herein, refers to compounds that are not substantiallyaltered when subjected to conditions to allow for their production,detection, and, in some aspects, their recovery, purification, and usefor one or more of the purposes disclosed herein.

In some chemical structures herein, substituents are shown attached to abond which crosses a bond in a ring of the depicted molecule. This meansthat one or more of the substituents may be attached to the ring at anyavailable position (usually in place of a hydrogen atom of the parentstructure). In cases where an atom of a ring so substituted has twosubstitutable positions, two groups may be present on the same ringatom. When more than one substituent is present, each is definedindependently of the others, and each may have a different structure. Incases where the substituent shown crossing a bond of the ring is —R,this has the same meaning as if the ring were said to be “optionallysubstituted” as described in the preceding paragraph.

As used herein, the term “catalyst” refers to a substance the presenceof which increases the rate of a chemical reaction, while not beingconsumed or undergoing a permanent chemical change itself.

Renewable sources means a source of carbon and/or hydrogen obtained frombiological life forms that can replenish itself in less than one hundredyears.

Renewable carbon means carbon obtained from biological life forms thatcan replenish itself in less than one hundred years.

Recycled sources mean carbon and/or hydrogen recovered from a previoususe in a manufactured article.

Recycled carbon means carbon recovered from a previous use in amanufactured article.

Green constituents means the carbon atoms and hydrogen atoms fromrenewable sources and from recycled sources in a material.

Green carbon means the total of renewable carbon and recycled carbon ina material.

Biodegradability and biodegradable refers to the ability of a materialto be broken down (decomposed) rapidly by the action of living organismssuch as bacteria, fungi, microorganisms or other biological meanswherein rapidly typically less than 10 years, 5 years, for 2 years.

Sustainable material and sustainable polymer means a biodegradablematerial and polymer, respectively, that is derived at least in part forgreen sources and has a percentage of green substituents equal to aminimum of 10%, and more typically 20%, 50%, 75%, 90%, 95%, or 100% ofthe total amount of carbon and hydrogen in the material.

As used herein, the term “about” preceding one or more numerical valuesmeans the numerical value ±5%. It should be understood that reference to“about” a value or parameter herein includes (and describes) aspectsthat are directed to that value or parameter per se. For example,description referring to “about x” includes description of “x” per se.

Further, it should be understood that reference to “between” two valuesor parameters herein includes (and describes) aspects that include thosetwo values or parameters per se. For example, description referring to“between x and y” includes description of “x” and “y” per se.

The mass fractions disclosed herein can be converted to wt. % bymultiplying by 100.

Biogenic Content and Sourcing of the bPL Monomer

The polymer of this invention will use bPL that can be produced from EOand CO according to the following general reaction schemes shown inFIGS. 1 and 2. In addition in this invention at least one of the EOand/or CO used to produce the bPL monomer will have a bio-content of atleast 10% and preferably at least 20%, at least 30%, at least 40%, atleast 50%, at least 60%, at least 70%, at least 80%, at least 90%, atleast 95%, at least 99%, or 100%.

The comonomers used in addition to the bPL monomers may have containcarbon with a significant bio-content. In some variation the comomersmay have a bio-content of at least 10% and preferably at least 20%, atleast 30%, at least 40%, at least 50%, at least 60%, at least 70%, atleast 80%, at least 90%, at least 95%, at least 99%, or 100%.

In variations of the foregoing, the resulting bPL copolymer will abio-content of greater than 0%, and less than 100%. In certainvariations of the foregoing, the polymer has a bio-content of at least10%, at least 20%, at least 30%, at least 40%, at least 50%, at least60%, at least 70%, at least 80%, at least 90%, at least 95%, at least99%, at least 99.5%, at least 99.9%, or 100%.

In this aspect of the invention the EO undergoes a carbonylationreaction, e.g., with CO, in the presence of a carbonylation catalyst toproduce the bPL monomer for production of the bPL based copolymer.

In the carbonylation reaction system, EO can be converted to bPL by acarbonylation reaction, as depicted in the reaction scheme below.

The chemistry involved in a carbonylation reaction system can include,but are not limited to, the following three reactions: (1) CO+EO to bPL;(2) EO to acetaldehyde; (3) bPL to succinic anhydride. The conversionsfor the three reactions may vary depending on many factors includingamount of reactants, amount of catalyst, temperature, pressure, flowrate, etc.

The carbonylation methods may utilize a metal carbonyl-Lewis acidcatalyst such as those described in U.S. Pat. No. 6,852,865. In otheraspects, the carbonylation step is performed with one or more of thecarbonylation catalysts disclosed in U.S. patent application Ser. No.10/820,958; and Ser. No. 10/586,826. In other aspects, the carbonylationstep is performed with one or more of the catalysts disclosed in U.S.Pat. Nos. 5,310,948; 7,420,064; and 5,359,081. Additional catalysts forthe carbonylation of epoxides are discussed in a review in Chem.Commun., 2007, 657-674. The entirety of each of the preceding referencesis incorporated herein by reference.

The carbonylation catalyst feed can be pumped under CO pressure to helpensure stability of the catalyst and can be cooled, optionally alongwith the feed, below ambient temperature to ensure stability.Carbonylation catalyst can arrive to the carbonylation catalyst sourceas either solids, that may be blanketed under CO or a suitable inertgas) or in solution of solvent such as hexane or THF. The carbonylationcatalyst feed can be pumped under CO pressure to help ensure stabilityof the catalyst and can be cooled, optionally along with the feed, belowambient temperature to ensure stability.

In yet other variations, the systems/processes provided to practice themethod herein are also configured to manage and integrate heat produced.The carbonylation reaction to produce bPL and the polymerizationreaction to produce bPL based copolymer are exothermic. Thus, the heatgenerated from the exothermic unit operations, such as the carbonylationreactor and polymerization reactor can be captured and used for coolingin endothermic unit operations, such as the distillation apparatus andthermolysis reactor. For example, in some variations of the systems andmethods provided herein, steam may be generated in heat transferequipment (e.g., shell and tube heat exchanger and reactor coolingjacket) via a temperature gradient between process fluid andwater/steam. This steam can be used for heat integration betweenexothermic and endothermic unit operations. In other variations of thesystems and methods provided herein, other suitable heat transfer fluidsmay be used.

In other variations, heat integration may be achieved by combiningcertain unit operations. For example, heat integration may be achievedby combining polymerization of bPL and vaporization of the solvent(e.g., THF) from the distillation column within a single unit operation.In such a configuration, the heat liberated from the bPL polymerizationreaction is used directly to vaporize the solvent in the distillationapparatus, and the output of the unit produces PPL. In other variations,the heat liberated from the polymerization reaction can be exported toother systems at the same production site. The distillation apparatusmay recover at least a portion of the carbonylation catalyst present inthe bPL product stream using a multi-solvent system.

The EO and CO preferably have a concentration of water and oxygen lessthan about 500 ppm, less than about 250 ppm, less than about 100 ppm,less than about 50 ppm, less than about 10 ppm, less than about 2 ppm,or less than 1 ppm.

The carbonylation reactor may be a continuous reactor, such as acontinuous stirred tank reactor (CSTR). Other reactors described herein,such as batch reactors, plug flow reactors (PFR), and semi-batchreactors may also be employed.

In certain variations, the reactor is equipped with an external cooler(heat exchanger). In some variations, the carbonylation reactionachieves a selectivity of bPL above 99%.

The post-isolation bPL product stream may have any concentration of bPL,solvent, EO, CO, by-products (such as acetaldehyde and succinicanhydride), carbonylation catalyst, or carbonylation catalyst componentsdescribed herein. In some aspects, the mass fraction of bPL in thepost-isolation bPL product stream can be about 0.1 to 0.4, or the molefraction of bPL in the post-isolation bPL product stream can be about0.1 to about 0.4. The post-isolation bPL product stream can also includeother components including unreacted EO (in mass fraction of about 0.005to 0.1), unreacted CO (in mass fraction of about 0.0005 to 0.001, or atmost about 0.002), acetaldehyde (in mass fraction of about 0.0005 to0.001, or at most about 0.002), succinic anhydride (in mass fraction ofabout 0.0005 to 0.01, or at most about 0.02), carbonylation catalyst,carbonylation catalyst, and the remainder solvent. In some aspects, thepost-isolation bPL product stream from the carbonylation catalystrecycling system can have a temperature of about 20° C. to about 60° C.In some aspects, the post-isolation bPL product stream can have apressure of about 1 to about 5 bar.

The bPL production system/production process may receive additionalcomponents comprising diluents which do not directly participate in thechemical reactions of EO. The diluents may include one or more inertgases (e.g., nitrogen, argon, helium and the like) or volatile organicmolecules such as hydrocarbons, ethers, and the like. The reactionstream may comprise hydrogen, CO of carbon dioxide, methane, and othercompounds commonly found in industrial CO streams. Such additionalcomponents may have a direct or indirect chemical function in one ormore of the processes involved in the conversion of EO to bPL andvarious end products. CO may be provided in a mixture with hydrogen fromrenewable sources such as syngas.

Further details of methods and process for the production of EO bycarbonylation with CO are disclosed in U.S. Ser. No. 15/197,838 filedJun. 30, 2016 the contents of which is herein incorporated by referencein its entirety.

bPL Based Copolymer Composition

In one embodiment, the co-polymer is produced by ring openingpolymerization of beta-propiolactone and a co-monomer. A wide variety ofcomonomers may be used with the bPL monomer and will generally be thosecomonomers that will add biodegradability to the resulting copolymer.

In addition to biodegradability and bio-content, comonomers andadditives that can impart other desired characteristics into theresulting bPL based copolymer. Of particular interest are phase behaviorand mechanical properties. A wide variety of additives may be used. Suchadditives include flame retardants, plasticizers, pigments, heat andlight stabilizers, fillers and fiber reinforcement.

Suitable comonomer include lactone comonomers having a higher number ofcarbon atoms than beta-propiolactone, in particular beta-lactones),anhydrides, and alcohols. Specific examples of suitable compounds toprovide the comonomers include diols, caprolactone and lactic acid.

In some aspects, the co-monomer is a higher beta-lactone having agreater number of carbon atoms that bPL and herein referred to as ahigher beta-lactone. Suitable higher beta-lactones for theco-polymerization include beta-butyrolactone, beta-valerolactone,beta-heptanolactone, beta-tridecanolactone,cis-3,4-dimethyloxetan-2-one, 4-(but-3-en-1-yl)oxetan-2-one,4-(butoxymethyl)-2-oxetanone,4-[[[(1,1-dimethylethyl)dimethylsilyl]oxy]methyl]-2-oxetanone,4-[(2-propen-1-yloxy)methyl]-2-oxetanone,4-[(benzoyloxy)methyl]-2-Oxetanone.

In some aspects of this invention, the co-monomer is a cyclic anhydride.In preferred aspects, the cyclic anhydrides include succinic anhydride,and maleic anhydride. In some aspects of this invention, the co-monomeris a cyclic anhydride. In preferred aspects, the cyclic anhydridesinclude succinic anhydride, and maleic anhydride.

The bPL based copolymers produced by this invention will have thestructure shown below:

In some embodiments, the co-polymerization of beta-lactones and cyclicanhydride is performed in the presence of polymerization initiator. Thepolymerization initiator initiates the ring opening polymerization ofbeta-lactones and cyclic anhydrides to produce co-polymers. A broadrange of polymerization catalysts can be used for the initiation of thering opening polymerization.

In some aspects of this invention the polymerization initiator is anionic initiator. In variations of this aspect, the ionic initiator hasthe general formula of M″X where M″ is cationic and X is anionic.

M″ is selected from the group consisting of Li+, Na+, K+, Mg2+, Ca2+,and Al3+. In some embodiments, M″ is Na+. In some embodiments, M″ is anorganic cation. In some embodiments, the organic cation is selected fromthe group consisting of quaternary ammonium, imidazolium, andbis(triphenylphosphine)iminium. In some embodiments, the quaternaryammonium cation is tetraalkyl ammonium.

X is a nucleophilic anion. Suitable nucleophilic anions include, but notlimited to, compounds comprising at least one carboxylate group, atleast one alkoxide group, at least one phenoxide group, and combinationthereof. In some embodiments, the nucleophilic anion is selected fromthe group consisting of halides, hydroxide, alkoxide, carboxylate, andcombination thereof. In some embodiments, the ionic initiator is sodiumacrylate. In some embodiments, the ionic initiator is tetrabutylammoniumacrylate.

In some embodiments, the polymerization is performed in the presence ofa solvent. The solvent may be selected from any solvent, and mixtures ofsolvents.

Suitable solvents for the polymerization with cyclic anhydride monomersinclude methylene chloride, chloroform, tetrahydrofuran, sulfolane,N-methyl pyrrolidone, diglyme, triglyme, tetraglyme, and dibasic esters.

In one embodiment, said co-polymer is produced by reactingbeta-propiolactone and an alcohol comprising at least two hydroxylgroups. Although, applicants are not bound to any theory as to how theco-polymer of beta-lactone and the alcohol comprising at least twohydroxyl groups, beta-propiolactone may react with the alcohol to form acarboxylic acid comprising at least two carboxylic acid groups as shownin the below scheme. The carboxylic acid having at least two carboxylicacid groups may further react with the alcohol having at least twohydroxyl groups by condensation polymerization to produce theco-polymer.

In variations of this embodiments, the alcohol is a diol. In someembodiments, suitable diols include ethylene glycol, propylene glycol,1,4-butanediol, diethylene glycol, bis(hydroxymethyl)octadecanol and1,6-hexanediol.

In further variation of this embodiment, the reaction can be conductedin the presence of a solvent. In some embodiments, suitable solventsinclude toluene, xylene and mesitylene. In some embodiments, thereaction setup allows continuous removal of water formed during theesterification reaction. In certain variations, the polymer chains haveopposing end groups of an initiator and a cation. In other variations,the initiator comprises an anionic nucleophile.

The suitable anionic nucleophiles include R^(x)O⁻, R^(x)C(═O)O⁻,R^(x)S⁻, R^(x)O(C═O)O⁻, halide (e.g., Br⁻, I⁻, Cl⁻), R^(x)(SO₂)O⁻ andPR^(x) ₃O⁻, wherein each R^(x) is, independently, selected fromhydrogen, optionally substituted aliphatic, optionally substitutedheteroaliphatic, optionally substituted aryl and optionally substitutedheteroaryl.

In certain aspects where the anionic nucleophile is R^(x)C(═O)O⁻, R^(x)is selected from optionally substituted aliphatic, fluorinatedaliphatic, optionally substituted heteroaliphatic, optionallysubstituted aryl, fluorinated aryl, and optionally substitutedheteroaryl. For example in certain aspects the initiator may beCH₂═CHCO₂—, CH₃CO₂ ⁻, or CF₃CO₂ ⁻.

In certain aspects where the initiator is R^(x)O⁻, R^(x) is selectedfrom optionally substituted aliphatic, optionally substitutedheteroaliphatic, optionally substituted aryl, and optionally substitutedheteroaryl. For example, in certain aspects the initiator is hydroxide,methoxide, or ethoxide.

In some aspects the cation is selected from the group of inorganic andorganic cations given above.

A wide variety of other polymerization initiators and catalyst may beused. Any suitable polymerization initiators and/or catalysts may beused to convert the bPL monomer and the comomers into the copolymerproduct stream entering the co-polymer production system/productionprocess into a co-polymer product stream.

In addition to the following description suitable catalysts, initiators,additives and solvent for the polymerization of the bPL monomer and thecomonomers can be found in U.S. Ser. No. 15/197,838 filed Jun. 30, 2016the contents of which is herein incorporated by reference in itsentirety.

Other Catalysts suitable for the ring-opening polymerization step of themethods disclosed herein are disclosed, for example, in: Journal of theAmerican Chemical Society (2002), 124(51), 15239-15248 Macromolecules,vol. 24, No. 20, pp. 5732-5733, Journal of Polymer Science, Part A-1,vol. 9, No. 10, pp. 2775-2787; Inoue, S., Y. Tomoi, T. Tsuruta & J.Furukawa; Macromolecules, vol. 26, No. 20, pp. 5533-5534;Macromolecules, vol. 23, No. 13, pp. 3206-3212; Polymer Preprints(1999), 40(1), 508-509; Macromolecules, vol. 21, No. 9, pp. 2657-2668;and Journal of Organometallic Chemistry, vol. 341, No. 1-3, pp. 83-9;and in U.S. Pat. Nos. 3,678,069, 3,169,945, 6,133,402; 5,648,452;6,316,590; 6,538,101; and 6,608,170. The entirety of each of which ishereby incorporated herein by reference.

The polymerization process may further comprise a polymerizationinitiator including but not limited to amines, polyamines, phosphinesamongst others. Further, a variety of polymerization initiators may beused in the polymerization process, including by not limited tocarbonates of alkali- and alkaline earth metals. In certain aspects,suitable polymerization initiators include carboxylate salts of metalions or organic cations. In certain aspects, a polymerization initiatoris combined with the production stream containing bPL. In certainaspects, the molar ratio of the polymerization initiator to the bPL inthe production stream is about 1:15000. In certain aspects, the molarratio of polymerization intiator:bPL is about 1:100, 1:10000, 1:1000,1:20000 or a range including any two of these ratios.

The polymerization initiator may comprises a carboxylate salt, thecarboxylate has a structure such that upon initiating polymerization ofbPL, the polymer chains produced have an acrylate chain end. In certainaspects, the carboxylate ion on a polymerization initiator is theanionic form of a chain transfer agent used in the polymerizationprocess.

In some aspects, the homogeneous polymerization initiator is aquaternary ammonium salt (for example, tetrabutylammonium (TBA)acrylate, TBA acetate, trimethylphenylammonium acrylate, ortrimethylphenylammonium acetate) or a phosphine (for example,tetraphenyl phosphonium acrylate).

In some aspects, the catalyst is tetrabutylammonium acrylate, sodiumacrylate, potassium acrylate, iron chloride, tetrabutylammonium acetate,trimethylphenylammonium acrylate, trimethylphenylammonium acetate, ortetraphenyl phosphonium acrylate.

In some aspects, the homogeneous polymerization initiator is added to apolymerization reactor as a liquid. In other aspects it is added as asolid, which then becomes homogeneous in the polymerization reaction. Insome aspects where the polymerization initiator is added as a liquid,the polymerization initiator may be added to the polymerization reactoras a melt or in any suitable solvent. For example, in some variationsmolten bPL is used as a solvent.

In some aspects, the solvent for the polymerization initiator isselected such that the initiator is soluble, the solvent does notcontaminate the product polymer, and the solvent is dry. In certainvariations, solid PPL is added to a polymerization reactor, heated aboveroom temperature until liquid, and used as the polymerization initiatorsolvent.

In some variations the process uses polymerization catalyst as describedbelow and as further described in U.S. Ser. No. 15/197,838 the contentsof which have been incorporated by reference.

In some aspects of the invention the catalyst comprises a carboxylatesalt as a homogeneous polymerization catalyst.

In some aspects, the catalyst is a heterogeneous polymerization catalystin the form of a solid-supported quaternary ammonium salt (for example,tetrabutylammonium (TBA) acrylate, TBA acetate, trimethylphenylammoniumacrylate, or trimethylphenylammonium acetate) or a phosphine (forexample, tetraphenyl phosphonium acrylate), iron chloride.

In addition to those already mentioned the polymerization process mayinclude one or more of solvents including hydrocarbons, ethers, esters,ketones, nitriles, amides, sulfones, halogenated hydrocarbons, and thelike. In certain aspects, the solvent is selected such that thecopolymer product stream is soluble in the reaction medium. The solventsmay also comprise Lewis bases of low to moderate polarity.

What is claimed is:
 1. A copolymer comprising beta-propiolactonemonomers and at least one co-monomer selected from the group consistingof lactic acid and an alcohol having greater than two hydroxyl groupswherein the copolymer contains an anionic nucleophile and cationic chainends.
 2. The copolymer of claim 1, wherein the comonomer has abio-content.
 3. The copolymer of claim 1, wherein the comonomer has abio-content of at least 50%.
 4. The copolymer of claim 1, wherein thecopolymer has a bio-content of at least 50%.
 5. The copolymer of claim1, wherein the anionic nucleophile is at least one compound with theformula R^(x)O⁻, R^(x)C(═O)O⁻, R^(x)S⁻, R^(x)O(C═O)O⁻, R^(x)(SO₂)O⁻ andPRF^(x) ₃O⁻, wherein each R^(x) is, independently, selected fromhydrogen, optionally substituted aliphatic, optionally substitutedheteroaliphatic, optionally substituted aryl and optionally substitutedheteroaryl.
 6. The copolymer of claim 5, wherein R^(x)O⁻, R^(x) isselected from optionally substituted aliphatic, optionally substitutedheteroaliphatic, optionally substituted aryl, and optionally substitutedheteroaryl.
 7. The copolymer of claim 6, wherein the anionic nucleophileis a hydroxide, methoxide, and/or ethoxide.
 8. The copolymer of claim 5,wherein the anionic nucleophile is a halide.
 9. The polymer of claim 5,wherein the anionic nucleophile is at least one compound with theformula CH₂═CHCO²⁻, CH₃CO₂ ⁻, or CF₃CO₂ ⁻.
 10. The polymer of claim 5,wherein the cation is selected from the group consisting of Li⁺, Na⁺,K⁺, Mg²⁺, Ca²⁺, Al³⁺, and Na⁺.
 11. The copolymer of claim 5, whereincation is an organic cation.
 12. The copolymer of claim 11, wherein theorganic cation is selected from the group consisting of quaternaryammonium, imidazolium, bis(triphenylphosphine)iminium and tetraalkylammomum.
 13. The copolymer of claim 1, wherein the copolymer it is formsat least part of a sanitary product.
 14. The copolymer of claim 1,wherein the copolymer is formed into at least part of a structuralproduct.
 15. A linear copolymer comprising chains of propiolactonemonomer units and at least one co-monomer derived from at least onehigher beta lactone moiety wherein the higher beta lactone moiety isderived from a beta lactone other than propiolactone and wherein thepolypropiolactone monomer units are produced by the decyliztion ofbeta-propiolactone derived from the carbonylation of ethylene oxide withcarbon monoxide using ethylene oxide that has a bio-content of at least10% and using carbon monoxide that optionally has a bio-content greaterthan 10%.
 16. The copolymer of claim 15, wherein the ethylene oxide hasa bio-content of at least 75% and preferably at least 95% and optionallythe carbon monoxide has a bio-content of at least 75% and preferably atleast 95%.
 17. The copolymer of claim 15, wherein the copolymer isformed into at least part of a sanitary product.
 18. The copolymer ofclaim 15, wherein the copolymer is formed into a structural product.